Abstract

A general motif of the crystal structure of [Rh(NH3)5Cl]2[Re6S8(CN)6]·3H2O is examined, and the cluster anions are found to form a pseudo-hexagonal sublattice. The thermal decomposition of [Rh(NH3)5Cl]2[Re6S8(CN)6]·3H2O is studied, and it is shown that in helium atmosphere thermolysis occurs through the formation of intermediate amorphous phases. The final product obtained at 1200°C is a disordered single-phase solid solution of Re0.75Rh0.25 based on the structure of rhenium. Powder X-ray diffraction data for solid solutions in the system of Rh-Re are surveyed. It is demonstrated that the data for phases prepared by the thermal decomposition of coordination compounds better match the theoretical state diagram than the experimental one. The dependence of atomic volume on the composition of solid solutions of RexRh1−x is derived.

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